Desiccant capability of organic xerogels: Surface chemistry vs porous texture

Resorcinol-Formaldehyde xerogels are organic polymers that can be easily tailored to have specific properties. These materials are composed of carbon, hydrogen and oxygen, and have a surface that is very rich in oxygen functionalities, and is therefore very hydrophilic. Their most interesting feature is that they may have the same chemical composition but a different porous texture. Consequently, the influence of porous characteristics, such as pore volume, surface area or pore size can be easily assessed. In this work, a commonly used desiccant, silica gel, is compared with organic xerogels to determine their rate and capacity of water adsorption, and to evaluate the role of surface chemistry versus porous texture. It was found that organic xerogels showed a higher rate of moisture adsorption than silica gel. Pore structure also seems to play an important role in water adsorption capacity. The OX-10 sample, whose porosity was mainly composed of micro-mesoporosity displayed a water adsorption capacity two times greater than that of the silica gel, and three times higher than that of the totally macroporous xerogel OX-2100. The presence of feeder pores (mesopores) that facilitate the access to the hydrophilic surface was observed to be the key factor for a good desiccant behaviour. Neither the total pore volume nor the high surface area (i.e. high microporosity) of the desiccant sample, is as important as the mesopore structure.

Effect of Cyclic Topology on Charge-Transfer Properties of Organic Molecular Semiconductors: The Case of Cycloparaphenylene Molecules

We have studied the role played by cyclic topology on charge-transfer properties of recently synthesized π -conjugated molecules, namely the set of [n]cycloparaphenylene compounds, with n the number of phenylene rings forming the curved nanoring. We estimate the charge-transfer rates for holes and electrons migration within the array of molecules in their crystalline state. The theoretical calculations suggest that increasing the size of the system would help to obtain higher hole and electron charge-transfer rates and that these materials might show an ambipolar behavior in real samples, independently of the different mode of packing followed by the [6]cycloparaphenylene and [12]cycloparaphenylene cases studied.

THE DESIGN AND SYNTHESIS OF SILOXANE PRECURSORS FOR CHIRAL PERIODIC MESOPOROUS ORGANOSILICA MATERIALS

The development of cost-effective and reliable methods for the synthesis and separation of asymmetric compounds is paramount in helping to meet society’s ever-growing demand for chiral small molecules. Of these methods, chiral heterogeneous supports are particularly appealing as they allow for the reuse of the chiral source. One such support, based on the synergy between chiral organic units and structurally stable inorganic silicon scaffolds are periodic mesoporous organosilicas (PMOs). In the work described herein, I examine some of the factors governing the transmission of chirality between chiral dopants and prochiral bulk phases in chiral PMO materials. In particular, the exploration of 1,1’-binaphthalene-bridged chiral dopants with a focus on the point of attachment into the materials. Moreover, the effects of ordering in the materials are examined and reveal that chirality transfer is more facile in materials with molecular-scale order then those containing amorphous walls. Secondly, the issues surrounding the synthesis and purification of aryl-triethoxysilanes as siloxane precursors are addressed. Both the introduction of a two-carbon linker and the direct attachment of allyl and mixed allyldiethoxysilane species are explored. This work demonstrates that allyldiethoxysilanes are ideal, in that they are stable enough to permit facile synthesis, while still being able to hydrolyze completely to produce well-ordered materials. Lastly, the production of new bulk phases for chiral PMO materials is examined by introducing new prochiral nitrogen-containing siloxane precursors. Biphenyldiamine and bipyridine-bridged siloxane precursors are readily synthesized on reasonable scales. Their use as the bulk siloxane precursor in the production of PMO materials however, is precluded by insufficient gelation and additional siloxane precursors are necessary for the production of ordered materials. In addition to the research detailed above that forms the body of this thesis, two short works are appended. The first details the production of polythiophene assemblies mediated through coordination nanospaces, while the second explores the production of N-heterocyclic carbene functionalized gold nanoparticles through ligand exchange.

Synthesis, Modification, and Application of Siloxane Materials for Environmental Sensing

As human populations and resource consumption increase, it is increasingly important to monitor the quality of our environment. While laboratory instruments offer useful information, portable, easy to use sensors would allow environmental analysis to occur on-site, at lower cost, and with minimal operator training. We explore the synthesis, modification, and applications of modified polysiloxane in environmental sensing. Multiple methods of producing modified siloxanes were investigated. Oligomers were formed by using functionalized monomers, producing siloxane materials containing silicon hydride, methyl, and phenyl side chains. Silicon hydride-functionalized oligomers were further modified by hydrosilylation to incorporate methyl ester and naphthyl side chains. Modifications to the siloxane materials were also carried out using post-curing treatments. Methyl ester-functionalized siloxane was incorporated into the surface of a cured poly(dimethylsiloxane) film by siloxane equilibration. The materials containing methyl esters were hydrolyzed to reveal carboxylic acids, which could later be used for covalent protein immobilization. Finally, the siloxane surfaces were modified to incorporate antibodies by covalent, affinity, and adsorption-based attachment. These modifications were characterized by a variety of methods, including contact angle, attenuated total reflectance Fourier transform infrared spectroscopy, dye labels, and 1H nuclear magnetic resonance spectroscopy. The modified siloxane materials were employed in a variety of sensing schemes. Volatile organic compounds were detected using methyl, phenyl, and naphthyl-functionalized materials on a Fabry-Perot interferometer and a refractometer. The Fabry-Perot interferometer was found to detect the analytes upon siloxane extraction by deformation of the Bragg reflectors. The refractometer was used to determine that naphthyl-functionalized siloxanes had elevated refractive indices, rendering these materials more sensitive to some analytes. Antibody-modified siloxanes were used to detect biological analytes through a solid phase microextraction-mediated enzyme linked immunosorbent assay (SPME ELISA). The SPME ELISA was found to have higher analyte sensitivity compared to a conventional ELISA system. The detection scheme was used to detect Escherichia coli at 8500 CFU/mL. These results demonstrate the variety of methods that can be used to modify siloxanes and the wide range of applications of modified siloxanes has been demonstrated through chemical and biological sensing schemes.

Catalytic wet peroxide oxidation: a route towards the application of hybrid magnetic carbon nanocomposites for the degradation of organic pollutants. A review

Several motivations have prompted the scientific community towards the application of hybrid magnetic carbon nanocomposites in catalytic wet peroxide oxidation (CWPO) processes. The most relevant literature on this topic is reviewed, with a special focus on the synergies that can arise from the combination of highly active and magnetically separable iron species with the easily tuned properties of carbon-based materials. These are mainly ascribed to increased adsorptive interactions, to good structural stability and low leaching levels of the metal species, and to increased regeneration and dispersion of the active sites, which are promoted by the presence of the carbon-based materials in the composites. The most significant features of carbon materials that may be further explored in the design of improved hybrid magnetic catalysts are also addressed, taking into consideration the experimental knowledge gathered by the authors in their studies and development of carbon-based catalysts for CWPO. The presence of stable metal impurities, basic active sites and sulphur-containing functionalities, as well as high specific surface area, adequate porous texture, adsorptive interactions and structural defects, are shown to increase the activity of carbon materials when applied in CWPO, while the presence of acidic oxygen-containing functionalities has the opposite effect.

Morphology Change of C60 Islands on Organic Crystals Observed by Atomic Force Microscopy

Organic-organic heterojunctions are nowadays highly regarded materials for light-emitting diodes, field-effect transistors, and photovoltaic cells with the prospect of designing low-cost, flexible, and efficient electronic devices.1-3 However, the key parameter of optimized heterojunctions relies on the choice of the molecular compounds as well as on the morphology of the organic-organic interface,4 which thus requires fundamental studies. In this work, we investigated the deposition of C60 molecules at room temperature on an organic layer compound, the salt bis(benzylammonium)bis(oxalato)cupurate(II), by means of noncontact atomic force microscopy. Three-dimensional molecular islands of C60 having either triangular or hexagonal shapes are formed on the substrate following a "Volmer-Weber" type of growth. We demonstrate the dynamical reshaping of those C60 nanostructures under the local action of the AFM tip at room temperature. The dissipated energy is about 75 meV and can be interpreted as the activation energy required for this migration process.

Organic properties of sediments and amino acids in iterstitial waters of ODP Holes 111-677A and 111-678B

The basement at Ocean Drilling Program (ODP) Sites 677 and 678 originated from the Galapagos spreading center of the Costa Rica Rift and has moved about 200 km over the last 6 m.y. (Fig. 1) (Shipboard Scientific Party, 1987, 1988; Scientific Drilling Party, 1987). Sediments about 300 m thick cover basement so young that basal sediments at Sites 677 and 678 have been reheated up to 60?-70?C at Site 677 and altered to limestone and/or chert (Shipboard Scientific Party, 1988). Sediments from both sites indicate (1) a high sedimentation rate (about 48 m/m.y.) and (2) biogenic silica and carbonate as the main constituents of sediments (Table 1) (Shipboard Scientific Party, 1988). Heatflow observations and measurements of interstitial water chemistry around the sites show that Site 677 is in a lower heatflow zone (166 mW/m**2; 1°12.14'N, 83°44.22'W) whereas Site 678 is located in a zone of higher heat flow (250 mW/m**2; 1°13.01'N, 83°43.39'W) (Langseth et al., 1988; Shipboard Scientific Party, 1988). In the flank hydrothermal systems, circulating solution is moving upward through the sedimentary column in zones of higher heat flow while it is moving downward in zones of lower heat flow (Anderson and Skilbeck, 1981). The chemistry of the interstitial waters is modified by several processes such as (1) diagenetic reactions and (2) advective and (3) diffusive transports of dissolved constituents. Analyses of Ca2+ and Mg2+ in interstitial waters from Sites 677 and 678 show that their profiles are mainly controlled by advective transport (Shipboard Scientific Party, 1988). In contrast, the interstitial-water profiles for NH4+, Si, and PO4[3-] are highly affected by reactions in the sediments. Site 677 offers a good opportunity to investigate amino acids in the interstitial waters because sediments of similar compositions have been deposited at constant rates of sedimentation. There are few previous works on amino acid distributions in interstitial waters (Henrichs and Parrington, 1979; Michaelis et al., 1982; Henrichs et al., 1984; Henrichs and Farrington, 1987; Ishizuka et al., 1988). In this chapter, we report (1) Rock-Eval analysis and (2) the composition of total hydrolyzable and dissolved free amino acids (THAA and DFAA, respectively) in the interstitial waters. Our objectives are to discuss (1) the possible origin of organic materials, (2) the characteristics of THAA and DFAA, and (3) their relationships in interstitial waters.

Geochemistry of organic carbon at DSDP Sites 75-530 and 75-532

CHN analyses of sediments and rocks sampled during DSDP Leg 75 in the South Atlantic have provided concentrations of organic carbon and atomic C/N ratios of organic matter from two sites. High values of organic carbon were measured in sediments deposited during Neogene and Cretaceous times at Site 530 in the Angola Basin; sediments deposited at other times contain less than 0.5% organic carbon. Development of the Benguela Current and associated upwelling-supported biological productivity is recorded in late Miocene to Holocene sediments which contain 1 to 7% organic carbon. These sediments include debris flows and turbidites composed of predominantly biogenic materials originally deposited on the Walvis Ridge and on the African continental margin. Organic-carbon-rich black shales containing up to 17% organic carbon occur in late Albian to Coniacian turbidite sequences. These Cretaceous black shale layers are commonly several centimeters thick and are separated by bioturbated fine-grained organic-carbon-poor turbidites which are usually much thicker. At Site 532 on the Walvis Ridge, biogenic sediments deposited between late Miocene and Holocene times contain 1 to 9% organic carbon. Fluctuations in the intensity of high biological productivity associated with the Benguela Current are preserved in alternating light and dark layers of sediments. C/N ratios of organic matter in sediments from both sites are typical of marine sources

Organic petrology of Neogene sediment from ODP Leg 117

Neogene sediments from three areas of the Northern Indian Ocean (Indus Fan, Owen Ridge, Oman Margin, ODP Leg 117) were studied in order to determine the amount, type, and preservation of organic matter as functions of the environments encountered. The work consisted of geochemical analyses on whole sediment (Total Organic Content and Rock Eval pyrolysis) and of petrographic studies on isolated organic matter by optical and scanning electron microscopy. In Indus Fan sediments, organic matter is present in low amounts, mainly as lignaceous fragments. A contrasting situation exists in Oman Margin sediments which are generally rich in amorphous autochtonous organic matter. Owen Ridge, located between Indus fan and Oman Margin areas, shows two phases of organic sedimentation as a consequence of the uplift of the ridge. The older phase (Oligocene to early or middle Miocene) is strongly influenced by detrital supply from the Indus, while the younger phase (middle Miocene to Pleistocene) is characterized by relatively high amounts of autochtonous organic matter. From a general point of view it appears that high amounts of organic matter are mainly due to good preservation of marine amorphous organic matter, such as in Oman Margin sediments and in upper pelagic levels of Indus Fan and Owen Ridge deposits. Low total organic carbon contents are correlated with low proportions of amorphous material in the total organic matter due to oxidizing conditions. This leads to a relative enrichment in components derived from resistant materials (lignin, chitin, or other resistant biopolymers) such as lignaceous fragments (Indus Fan) and/or fragments from benthic organisms and alveolate microplankton (Oman Margin).

Isotopic ratios and concentrations for mineral-associated and particulate organic fractions of sediment core Wilson_Lake samples

The flux of sediment and organic carbon from continents to the coastal ocean is an important factor governing organic burial in coastal sediments, and these systems preserve important records of environmental and biogeochemical conditions during past global change events. Burial of organic materials in coastal systems can be promoted by chemical resilience or through protection by association with mineral surfaces, but the role and influence of these processes on organic records from ancient sediments is poorly known. We studied sediment and organic matter burial as particulate organic matter (POM) and mineral-bound organic matter (MOM) in near-shore marine sediments from the Wilson Lake core (New Jersey, USA) that span the Paleocene-Eocene thermal maximum (PETM), a climatic perturbation 55.9 Myr ago. Our results show that distinct POM and MOM fractions can be isolated from sediments. Both fractions appear to be dominated by terrestrial material, but POM consisted primarily of recently synthesized material whereas MOM included a significant fraction of pre-aged organic matter from soils or ancient sediments. Variation in organic burial through the PETM is associated with changes in inorganic nitrogen burial, clay mineralogy, and clastic grain size that we associate with enhanced continental weathering, erosion and redeposition of ancient kaolinites, and eustatic sea level variation, respectively. These results provide a new perspective on factors governing carbon burial and carbon isotope records in ancient marine margin settings and offer information on rate and phasing of late Paleocene/early Eocene Earth system changes that may constrain interpretations of the cause of the PETM climate change event.

Low cost solar cells based on amorphous silicon electrodeposited from organic solvents : final technical report, September 1, 1978-August 31, 1979 /

"Work Performed Under Contract No. EY-76-S-03-0113-040."

Allen's commercial organic analysis; a treatise on the properties, modes of assaying, and proximate analytical examination of the various organic chemicals and products employed in the arts, manufactures, medicine, etc., with concise methods for the detection and estimation of their impurities, adulterations, and products of decomposition ...

Vols. 3-9 edited by W.A. Davis and Samuel S. Sadtler.

The Discovery, Development, and Mechanistic Investigations of Transition Metal-Catalyzed Organic Reactions

Thesis (Ph.D.)--University of Washington, 2016-06

Organic Semiconducing Thin Films: Device Applications and Beyond

Thesis (Master's)--University of Washington, 2016-06

Molecular dynamics simulation of organic-inorganic nanocomposites: Layering behavior and interlayer structure of organoclays

Isothermal-isobaric (NPT) molecular dynamics simulation has been performed to investigate the layering behavior and structure of nanoconfined quaternary alkylammoniums in organoclays. This work is focused on systems consisting of two clay layers and a number of alkylammoniums, and involves the use of modified Dreiding force field. The simulated basal spacings of organoclays agree satisfactorily with the experimental results in the literature. The atomic density profiles in the direction normal to the clay surface indicate that the alkyl chains within the interlayer space of montmorillonite exhibit an obvious layering behavior. The headgroups of long alkyl chains are distributed within two layers close to the clay surface, whereas the distributions of methyl and methylene groups are strongly dependent on the alkyl chain length and clay layer charge. Monolayer, bilayer, and pseudo-trilayer structures are found in organoclays modified with single long alkyl chains, which are identical to the structural models based on the measured basal spacings. A pseudo-quadrilayer structure, for the first time to our knowledge, is also identified in organoclays with double long alkyl chains. In the mixture structure of paraffin-type and multilayer, alkyl chains do not lie flat within a single layer but interlace, and also jump to the next layer in pseudo-trilayer as well as next nearest layer in pseudo-quadrilayer.